Photographic color elements containing uv absorbers



United States Patent 3,512,984 PHOTOGRAPHIC COLOR ELEMENTS CONTAINING UV ABSORBERS Hiroyuki Amano, Nobuo Tsuji, and Kazuo Shirasu, Ashigara-Kamigun, Kanagawa, Japan, assignors to lFuji Shashin Film Kahushiki Kaisha, Kanagawa,

apan No Drawing. Filed Jan. 16, 1967, Ser. No. 609,359 Int. Cl. G03c 1/84, 1/92 U..S. Cl. 9684 9 Claims ABSTRACT OF THE DISCLOSURE wherein M is an alkali metal; R is a bivalent organic radical selected from the group consisting of wherein R and R are selected from the group consisting of a hydrogen atom, an alkyl radical containing up to carbon atoms, {CH- wherein p is an integer of from 1 to 10, and

wherein q is an integer of from 1 to 3, and n indicates the degree of polymerization, and wherein said polymerization degree is such that the intrinsic viscosity of the polymer in formamide at 30 C. is from about 0.05 to about 2.0.

The present invention relates generally to color photography, and more particularly, to a photographic color element capable of protecting the color image obtained by color development from the action of ultraviolet radiations.

When a photographic image is exposed to ultraviolet radiations, the image will fade or be discolored in respouse to the intensity and the wave length of the ultraviolet radiations. Further, other materials present in the photographic element together with the materials formmg the photographic image are sometimes colored by ultraviolet radiations. Such action is mainly caused by the radiation of ultraviolet rays having a wavelength of 300- 400 nm. In order to prevent such action, ultraviolet absorbers are frequently incorporated in at least one layer of the photographic silver halide emulsion layers, intermediate layers, and protective layer, in the case of a printing paper, or in at least one layer of the photographic emulsion layers, intermediate layers, protective layer, and backing layer of a support, in the case of a transparent positive film.

However, there are drawbacks in the conventionally known ultraviolet absorbers such that when they are incorporated in a photographic silver halide emulsion layer, an intermediate layer, a protective layer, an under layer or a backing layer, almost the greater part of the ultraviolet absorbers are frequently dissolved out during photographic processing or water washing, and, hence, the effect thereof is weakened.

Therefore, the inventors have investigated variously to improve the drawbacks of the conventional ultraviolet absorbers and as a result thereof the inventors have found that a remarkable ultraviolet preventing effect can be obtained by incorporating in at least one of the photographic emulsion layers, intermediate layers, protective layer, under layer and backing layer of a photographic light sensitive color element a polysulfonamide, polyester, polycarbonate or polysulfonate containing the following structure:

SOzM S OaM wherein M represents an alkali metal.

The high molecular ultraviolet absorbers to be used in the present invention will be explained in detail.

When a 4,4'-diamino stilbene 2,2 disulfonate having the following structure formula:

is caused to react with a disulfonylchloride, the polysulfonamide having the above-described structure is obtained. As the disulfonylchloride used in this reaction there may be used m-benzene-disulfonylchloride,

ammO-smfisom and ClSOzCHz-CHzSOzCl When a 4,4-dioxystilbene 2,2 disulfonate having the following structural formula:

Patented May 19, 1970 3 such as, ClCOO(CH OCOCl (12:0-10), and a dichlorocarbonic acid ester of an aromatic diol shown by the general formula, ClCOOAr-OCOCl, wherein Ar represents an aromatic residual group. For example, there may be illustrated the following compounds:

This disulfonylchloride for producing the polysulfonate may be one employed in the case of producing the abovementioned polysulfonamide.

Thus, the high molecular ultraviolet absorbers of the present invention may be represented by the following wherein M represents an alkali metal; R represents an aromatic or an aliphatic bivalent residual groups, such as,

wherein R and R are hydrogen atoms or alkyl radicals containing up to 5 carbon atoms, {-CHfi wherein p is an integer from 1 to or 0 HzCHrO CH2 CH2- wherein q is an integer from 1 to 3 and It shows the polymerization degree.

These compounds may be easily prepared by conventional methods in particular by the usual interfacial condensation methods. For example, the above-illustrated polysulfonamide may be prepared by the following procedure. Sodium 4, 4-diaminostilbene2,2-sulfonate is dissolved into 2,5 equivalents of an aqueous solution of sodium hydroxide and, while cooling the resulting solution to a temperature lower than 10 C., a methylene chloride solution of m-benzene disulfonylchloride, in an equivalent to the above stilbene compound, is added into the solution with stirring. After 1.5 hours, the thus formed aqueous layer is separated from the methylene chloride layer and the former is subjected to dialysis for one night in a cellophane tube. When acetone is added into the thus dialyzed aqueous solution, a polymer product is precipitated, and this is separated and dried to provide the polysulfonamide.

The above-mentioned high molecular ultraviolet absorber of this invention may be used in the following manner. The high molecular ultraviolet absorbers are dissolved in water to provide an aqueous solution of from 0.1 to 5% by weight of the material. Into the resulting aqueous solution is added slowly an aqueous solution of gelatin. The proportion of the high molecular ultraviolet absorber is preferably from about 10 to 500' g. per 1 kg. of the gelatin. The thus prepared mixture of gelatin and high molecular ultraviolet absorber is applied to a photographic element as a protective layer, an intermediate layer, an under layer or a backing layer to serve as an ultraviolet preventing layer. Further, the high molecular ultraviolet absorber of this invention may be effectively incorporated directly in a photographic silver halide emulsion layer and, in this case, the above-defined additional amount is also preferable.

With regard to the influence of the molecular weight of the high molecular ultraviolet absorber of this invention, a better ultraviolet preventing effect can be obtained when the intrinsic viscosity of the high molecular ultraviolet preventing material of this invention in formamide at 30 C. is about 0.052.0.

In addition, the above-mentioned photographic emulsion is a conventional gelatino silver halide emulsion, but the present invention may also effectively be applied to the case where protective colloids other than gelatin are employed, such as, polyvinyl alcohol and polyvinyl acetal.

The following typical examples illustrate the results of the prevention of fading and the diffusion resistance for photographic color images obtained by using the high molecular ultraviolet absorbers of the present invention but the invention shall not be limited to these examples.

EXAMPLE 1 Compound 1: NEHOwHwH-Q-NHSOQ- so2 K SOQNS. S OgNfi Compound 2:

C CH=CHOSO2- so2 K SO Na SO Na Compound 3 l k SO Na S O Na Compound 4 (n is the polymerization degree) Compound 5 (control) SOBNa. SOaNfl NHI INHQCH=CHQNHf INm Into 100 g. of a 4% aqueous solution of each of the compounds 14 of this invention and compound 5 of a conventional ultraviolet absorber was added gradually 1 kg. of a 4% aqueous solution of gelatin and the resulting emulsion was applied to the surface of a film support and dried to provide a filter layer of 2.0 microns in thickness. Concerning the thus prepared film having a filter layer containing each compound, the state of each compound after the film is subjected to water washing (A), washing with an aqueous solution 3% sodium carbonate (B), or complete photographic processing (C) was observed. The results are shown in the following table.

REDUCTION IN TRANSMISSION DENSITY (370 n.m.)

Compound percent Time 1 2 3 4 5 From the above results it will be understood that while a conventional low molecular ultraviolet absorber having a diffusion tendency, such as compound 5, is almost dissolved from the gelatin layer by the washing step (A) or the complete photographic processing steps (C), the high molecular compounds l-4 of the present invention are scarcely dissolved and have good diffusion resistance. The complete photographic processings in the above experiments means the steps commonly employed in color paper processing, namely, the steps of developing, stopfixing, water-washing, bleach-fixing, water-washing, hardening, water-washing and drying.

Moreover, other high molecular compounds represented by the above-described structural Formulas 1-4 having different high molecular weights show almost same effects as the above-mentioned compounds as ultraviolet absorbers when the intrinsic viscosity thereof in formamide at 30.0 C. was in a range of 0.05-2.0.

EXAMPLE 2 To a baryta paper was applied a blue-sensitive silver iodobromide emulsion containing a yellow coupler, 3,5- dicarbosy-u-(4-stearoylamino benzoyl) acetanilide. The coupler was added as an alkaline aqueous solution thereof. Thereafter, a green-sensitive silver chloro-bromide emulsion containing a magenta coupler, l-(3-sulfo-4-phenoxyphenyl)-3-stearoyl-5-pyrazolone and a red-sensitive silver chloro-bromide emulsion containing a cyan coupler, N-noctadecyl-1-hydroxy-4-sulfo-2-naphthamide were applied to the thus formed blue-sensitive emulsion layer, in order, and then a protective layer 2.0 microns in thickness, was further applied thereto. The protective layer was formed by applying 1 kg. of an aqueous gelatin solution containing 100 g. of a 4% aqueous solution of a high molecular ultraviolet absorber of this invention having the structures 14 shown in Example 1.

After exposure, the thus prepared color printing paper was subjected to development in a developer containing N-ethyl-N-fl-hydroxyethyl-p-phenylene diamine, stop-fixing, water-washing, bleach-fixing, water-washing, hardening, water-washing and drying. Thereafter, the thus processed. printing paper was exposed for hours to a xenon tester and then the reduction in color density of the color image was measured in each case. The results are shown below.

The xenon tester which was used in the fading tests had a light source having a spectral distribution of energy and an intensity very similar to those of sunlight.

FADING PERCENTAGE OF COLOR IMAGE AFTER EXPO- SURE FOR 20 HRS. TO XENON TESTER Addition compound (percent) As is seen from the above results, the fading of color images was prevented or reduced by incorporating in the layer the high molecular ultraviolet absorber. Further, as could be anticipated naturally, when the high molecular ultraviolet absorber of this invention was incorporated in the intermediate layer between a first silver halide emulsion layer and a second silver halide emulsion layer, or in an intermediate layer, between the second silver halide emulsion layer and the third silver halide emulsion layer, instead of being incorporated in the protective layer, fading of the color image in the layer below the intermediate layer containing the ultraviolet absorber was prevented or reduced. Moreover, when a film base was used instead of baryta paper, almost same results were obtained.

EXAMPLE 3 To a baryta paper there were applied the blue-sensitive silver halide emulsion containing the yellow coupler, and the green-sensitive silver halide emulsion containing the magenta coupler, both as in Example 2, as bottom and middle layers respectively. As a top layer, there was applied the red-sensitive silver halide emulsion containing the cyan coupler, also as in Example 2, and the high molecular ultraviolet absorbing compounds of this invention having the formulas shown in Example 1, that is, compounds 1-4, in an amount of 50 g. of a 4% aqueous solution per 1 kg. of emulsion, to provide a multilayer light sensitive color element.

After exposure, the thus prepared light sensitive element was subjected to developing, stop-fixing, waterwashing, bleach-fixing, water washing, hardening, waterwashing and drying. Thereafter, the thus processed light sensitive element was exposed for 20 hours to a xenon tester, as in Example 2. Then the reduction in color image density was measured. The results are as follows:

FADING PERCENTAGE OF COLOR IMAGE AFTER EXPO- SURE FOR 20 HRS. TO XENON TESTER Addition compound (percent) None 1 2 3 4 As is seen from the results, a very large ultraviolet preventing effect was obtained by incorporating directly in a silver halide emulsion layer the high molecular ultraviolet absorber of this invention, without forming a separate ultraviolet preventing layer.

EXAMPLE 4 To the filter layer (under layer) containing each of compounds 14, which had been formed on a film sup- After exposure, the thus prepared multilayered light sensitive film was subjected to developing, stop-fixing, water-washing, bleach-fixing, water-washing, hardening, water-washing and drying. Thereafter, the thus processed film was exposed to a xenon tester for 20 hours. Exposure was from the back side of the support and the reduction in color image density in each case was measured. The results are shown in the following table.

FADING PERCENTAGE OF COLOR IMAGE AFTER EXPO- SURE FOR 20 HRS. TO XENON TESTER Addition compound (percent) As is seen from the experimental results, the fading of the color image in the case where no ultraviolet absorber of the present invention is incorporated in the under layer (the lowest filter layer) was prevented or reduced by the use of the ultraviolet absorber.

When such an ultraviolet absorber was incorporated in a backing layer of the support, instead of incorporating it in the under layer, almost same results were obtained.

Moreover, when the high molecular ultraviolet absorber of the present invention was incorporated in both a protective layer and an under layer (or a backing layer), almost the same fading prevention effect was obtained against light from the emulsion side and light from the back side.

What is claimed is:

1. A photographic light-sensitive color element having incorporated in at least one layer selected from the group consisting of silver halide emulsion layer, and. intermediate layer between silver halide emulsion layers and a protective layer on the surface of the silver halide emulsion layer, as an agent to minimize the undesired effects of ultraviolet radiation, at least one compound containing recurring structure selected from the following group:

Polysulfonamide wherein M is an alkali metal; R is a bivalent organic radical selected from the group consisting of wherein R and R are selected from the group consisting of a hydrogen atom, an alkyl radical containing up to 5 carbon atoms, {CH -h, wherein p is an integer of from 1 to 10, and tCH CH -O) CH CH wherein q is an integer of from 1 to 3, and n indicates the degree of polymerization, and wherein said polymerization degree is such that the intrinsic viscosity of said polymer in formamide at 30 C. is from about 0.05 to about 2.0.

2. A photographic light-sensitive color element having incorporated in at least one layer selected from the group consisting of a silver halide emulsion layer, an intermediate layer between silver halide emulsion layers and protective layer on the surface of a silver halide emulsion layer a polysulfonamide containing the following structure:

wherein M is an alkali metal; R is a bivalent organic radical selected from the group consisting of wherein R and R are selected from the group consisting of a hydrogen atom, an alkyl radical containing up to 5 carbon atoms, {-cH -h, wherein p is an integer of from 1 to 10, and %CH CH O-} CH CH wherein q is an integer of from 1 to 3, and n indicates the degree of polymerization, and wherein said polymerization degree is such that the intrinsic viscosity of said polymer in formamide at 30 C. is from about 0.05 to about 2.0.

3. A photographic light-sensitive color element having incorporated in at least one layer selected from the group consisting of a silver halide emulsion layer, an intermediate layer between silver halide emulsion layers and a protective layer on the surface of a silver halide emulsion layer a polyester containing the following structure:

wherein M is an alkali metal; R is a bivalent organic radical selected from the group consisting of wherein R and R are selected from the group consisting of a hydrogen atom, an alkyl radical containing up to carbon atoms, {CH l wherein p is an integer of from 1 to 10, and

O 2CH20 qCHzCH2 wherein q is an integer of from 1 to 3, and n indicates the degree of polymerization and wherein said polymerization degree is such that the intrinsic viscosity of said polymer in formamide at 30 C. is from about 0.05 to 2.0.

4. A photographic light-sensitive color element having incorporated in at least one layer selected from the group consisting of a silver halide emulsion layer, an intermediate layer between silver halide emulsion layers and a protective layer on the surface of a silver halide emulsion layer a polysulfonate containing the following structure:

sonvr so 3M wherein M is an alkali metal; R is a bivalent organic radical selected from the group consisting of l to @"Q g S W wherein R and R are selected from the group consisting of a hydrogen atom, an alkyl radical containing up to 5 carbon atoms, tong, wherein p is an integer of from 1 to 10, and

wherein q is an integer of from 1 to 3, and n indicates the degree of polymerization and wherein said polymerization degree is such that the intrinsic viscosity of said polymer in formamide at 30 C. is from about 0.05 to about 2.0

5. A photographic light-sensitive color element having incorporated in at least one layer selected from the group consisting of a silver halide emulsion layer, an intermemediate layer between silver halide emulsion layers and a protective layer on the surface of a silver halide emulsion layer a polycarbonate containing the following structure:

wherein M is an alkali metal; R is a bivalent organic radical selected from the group consisting of l il) wherein R and R are selected from the group consisting of a hydrogen atom, an alkyl radical containing up to 5 carbon atoms, {-CH 9- wherein p is an integer of from 1 to 10, and

wherein q is an integer of from 1 to 3, and It indicates the degree of polymerization, and wherein said polymerization degree is such that the intrinsic viscosity of said polymer in formamide at 30 C. is from about 0.05 to 2.0.

6. The photographic color element of claim 1, wherein said structure is SOz 7. The photographic color element of claim 1, wherein said structure is 'SO Na SOsNa 8. The photographic color element of claim 1, wherein said structure is {0-CH=CHOCO(OH2)4C0) SOaNa SOsNa 9. The photographic color element of claim 1, wherein said structure is SOaNa SOaNa References Cited UNITED STATES PATENTS 8/1966 Pattyn et al. 9682 RONALD H. SMITH, Primary Examiner U.S. Cl. X.R. 

